In this study, the three-dimensional ordered macroporous (3DOM) structure is applied to the preparation of the core-shell structure metal matrix composites. 3DOM Fe2O3, which was coated with different molar ratios of Co3O4, was successfully synthesized by inversing PS spheres colloidal crystal template and sol-gel methods, and subsequently characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), N-2 absorption-desorption isotherms, X-ray diffraction (XRD). The catalytic activities of 3DOM Fe2O3/xCo(3)O(4) core-shell composites, 3DOM Fe2O3, bulk Fe2O3 and bulk Fe2O3/Co3O4 on the thermal decomposition of ammonium perchlorate (AP) were investigated by differential scanning calorimeter (DSC). The results indicated that all products showed excellent catalytic activity. Among the samples investigated here, the 3DOM Fe2O3/0.70Co(3)O(4) exhibited the best catalytic activity, since the maximum peak temperature for the decomposition of the AP decrease to 308.5 degrees C. The enhanced catalytic performance of 3DOM Fe2O3/0.70Co(3)O(4) was attributed to its unique porous architecture, high surface area, Fe2O3-Co3O4 heterojunction and good adsorption capacity. Hence, 3DOM Fe2O3/0.70Co(3)O(4) was expected to be used as the promising catalysts in modifying the burning performance of AP-based composite propellant. (C) 2017 Elsevier B.V. All rights reserved.